Production of hydroxy ethers



United States Pate-nef() l CurtisWa Smith and Douglas G. Norton,-= Berkcleyfand "Development Company,

rf* 2,808,442 `Patented Oct. 1, 1957 'discoverythat theprimary and secondary alcoholsy-unff like tertiary alcohols, can Stake -partin the reaction, with the ethylenic compound and form hydroxyr ethers. '"aAs-fcatalyst for thenew--reactiongv one must Iuseanacid 5'/cap'ablel of -reactingwith they peroxide -employed"in-the f-{reaction/tolfform aperacid under the reaction conditions. 'I It- 'is also necessary that the acid'be a 'strong-1one, i, e. have an 'ionization' constant for theprst Ahydrogenzgr'eater l1;than-1f.86 l105 at125 Cfsince-otherwise hydroxy esters l`lare formed instead of the desired'hydroxy ethers Typical fli examples r(5f-'inorganicA acids jwhich fulfill these. require- `Hrnentsfand' arci elfec'tive catalysts for the new reactionare A :tungtsic lacid,'f`the polytungsticacids heterpolytungstic acids such as phosphotungstic acidfselenotungstic facid,

2,808,442 i"fPRODlZIGTION OFJHYDROXY-ETHERS ,George 'BQ `Paync,..Alban alif.,ffssignors `tti-...Shell Emeryville, Calif., a corporation of'Delaware .zz-This invention relates to the reaction-ofi ethylenic= com- -1fpounds'--with1iperoxide hydroxylating-v` agents v`under =con f trolled :conditions atwhichhydroxy ethers are f obtained .rras alproduct.

lihtu-n'gstomlyb'dic acid, f 'bisomotungstic f acid,- and the like,

fsnmolybdicfacid, vanadic acid; chromic acid, fslilfu'ricf acid,

tc. '-*Organicistrong acids such pas'l triuoroacetic, ytrichloomethanepho'sphonic acid, trichloroacetic,v p-toluenefsulat -least-one ethylenic double between two fcarl;1on atoms"oaliphatiocharacter, react .with-r.: peroxide .fhydroxylat-ing..@agents such zas hydrogen 1 peroxide .tol form` polyhydroxy L compounds by addition fof two hydroxyl-groups at .the ethylenicldoubleabond; A variety of;v dilerent -typ'es ofcatalystsA have-been1used in promotingf suchhydr'oxylations, aspointed out by.' Mugdan land=y Young -in the "(1949);,y ipa-ges 12988"-";l000.- L-BergsteinssonA patent-LU. S. 2,373,942dis`closes and-claims the vuseofftung'stioacid f "--ioatalysts which areiespecially advantageous hydroxylav tion promoters. i Such' hydroxylationsrhave been-carried out infaqueousmedia or in diiferenttypes of non-'reactive organic solvents.- In allxc'ases the products; aslfarly as we have beeable 'toA determine,- have been itheexpected v=f'polyhydroxy compounds or partialaestersz thereorfwhen the` hydroxylation has been. conducted-1 in l the presence of ac'o'rboxylicV acid. No 'productionof-hydroxyethers from L*the reaction of fethylenic compoundsl witl1lperoxide f hydroxylating` agents has s apparently i'beerrllreported `hitherto.

--vide a1 'methodl ofhconvertingfethylfenic'. compoundsvv to flhydroxiy Acthers by 'reactionl with peroxide Lhydroxylating wffagents. Y `l`A lparticular-11object is:thefcatalyticv reactionfof 1= an ethyleniccompoundvwith hydrogeni peroxidesinthe Y. presence of Aafprimary or.secondary:alcoholfunderfconditions rregulated to? promotevattachmenteof. a :hydroxyl group and anzether radical .on adjacent carbonzatomsv of As. is well-known, organicicompoundswhichlcontain bond, if. epa-double bond o'nic -acid-andlfalka'ne sulfonic acid 'areffalso'electiv catlysts.i0therl2types offhydroxylation catalysts Iarenot uitableii 'Thus,` '.osmium tetroxidej although loften@ incoreetl-y referredtof asformingosmic andlperosrniclacids s not. 'elective 1in the .new process -be'causefit apparently :if operates r`by 'a'.ldierent: mechanism' involving fiaddition of thelosmiumltetr'oxider to ."thfeffethylenicwbond or:l bonds hichpreclu'des the formation ofihydroxylethers. Tung- "stic :acid catalysts, :which expression is intended to include sthe .fheteropolyturigsticiacids,1:are'xpreferredl inf carry-ing ;;-:.out.:.the:reactio.because:.-they@have `less :tendency-than r otherz',peracideforminga catalysts torfpromote undesirable :aeoxidatiomzor decomposition. ofi-peroxidesa i touf oxygen.

Antlie ff essential .frequrern'entrt for fg'ood conversions o;-rhydrox`y: 1 ethers'` .ini 'accordance `with: ithefinvention is atxatrleast 10, moles; and more preferably about' A12 to ?:351.moles,- of-primaryror secondary al'coholslorfmixtures qthe'reofn-r bei fusedziperl mole;- of :peroxide employed. f lAs ."-.previously indicated; the :primaryv or; secondaryzralcohol nmusedcan bean ethylenic alcohol; in which. caseno'zother .i-ffethylenic,compound-need b e. present. :Wherea saturated 40Aprimary orzsecondaryLa-lcohol is used;anfethylenicscompoundmustbefpresent.- -Preferably; about' V10: tcrrabout Osmoles yof -such vsaturatedfalcoholy .arefu'sed'iper mole of 1 ethylenic tcompound. :About 0.5 t to about 5-,1 :preferably ryabout. e1 tofaboutzl, moles :ofrnon-l-alcoholic ethylenic compound are used per mole of peroxideicmployedn"1The 5 f overallfreactionmay berepresentedr by; thefollowingfequationriny which hydrogen Aperoxide-is used ra's illustrative of .the-peroxide which may be employed:

-iA'n importantobject of the present 'invntionisf `tti-prothe starting ethylenicicompoundl: Still'otherobjectsrand p --lRr-:OH-Rs `advantages of the process of the invention will :be apparent 50 0H `from the following description. l v y V The present invention is -basedx-upon-ther discovery "i"HO+`R?*CTR+RGHR 'Rii-iilino that; by the .proper combination ofcatalystf andwpropor- "-lRr R2 lOH Rif' Rn tions of reactants,` `hydroxy 'ethers, canfbesiobtainedf. as

where-R, R1, Rz,v Ra; R4 fand R5 represent hydrogenatoms products' in the '-reaction of -ethyleniccompounds-with 55foporganjcradica1s,

peroxides provided there is present-.-sucient of 'aipri- `alcohols arenot attackedas they-are in Athe-absenccqof It isdesirable to maintain in the reaction mixture a *high 'concentration ofsprimary and/or secondary,` alcohol, ""'theghydroxy ether of which it is'desired 'to produce. Preferably -a concentration of -such alcohol' lofratfleast percent by weight of thetotal reactionfmixturajand `lmore:preferably from -aboutg70 tofabout 9,9 percent, is -fused It isfespecially' desirable that the water content of l'themixture be kept as-low as possible;"preferalzvly, less 414132114367 nOles of Wate'n'exclusive of thatformed in the 'reaction,- a're present per mole of peroxide lemployed 'for v,litho-re'actioniif'Diluents which-are inert v`under thereac- YI1 ionlfconditio'ns or which undergo -.reactions 'whichdonot M interfere yVith thefor'r'n'ation of jthe'desired hydroxy 1@ther Vl orfethers :for` instance, organic 1solventsjforthereactants 7 Oraand productlsch assat'urated tertiary alcoholQethrsesl f tersiket'onesy.v etc.; fc'a'ne be present but' tg"enterally-'-z1`1=of"'110 gwadvantage. y `j` c f 1 mary` or secondary alcohol, which, if it is=anethylenic It is on this-account thatyth'e more diiculty oxidizablez tertiary alcohol-s-have-been.generally used when `carrying out-reactionswith suchrperoxide in solution in an1alcohol. It -wassurprisingato.nd,1there fore, that ethylenic compounds can be successfullyfreacted with peroxide in -the presence of primaryandsecondary alcohols without undesirable oxidation ofcsuchjalcohols. Apparently, in the presence of an ethylenic compound preferential reactionv ofHthe-"peroxide at the ethylenic linkage or linkages takes placeand--primary o r secondary ethylenic compounds. -Evenmore unexpectedlwas;the`

The reaction is preferably carried out with the reactantsv in the liquid phase at temperatures of the order of about C. to about 150 C. The higher the temperature, the shorter the time required for completion of the reaction, but temperatures in the range .of about 30 C. to about 75 C. are generally preferred. About 2 to 6 hours is usually suflicient under most conditions. Ordinary pressures are generally satisfactory for the reaction, but higher or lower pressures can also be used whether liquid or vapor phase reaction conditions are employed. Relatively small amounts of the strong acid catalysts are effective in the reaction. Amounts in the range of about 0.005 to 0.075 mole of acid per mole of the peroxide employed have been generally used, although somewhat larger amounts are usually not detrimental. Preferred proportions are 0.01 to 0.04 mole of strong acid catalyst Vper mole of peroxide.

The process can be carried out batchwise, continuously or intermittently. One suitable method of batch reaction is to mix the reactants and catalyst in the proper ratios Y and heat the mixture for the required time, after which the mixture can be worked up, for example, by distillation, to recover the hydroxyether produced from the unreacted starting materials and by-products (which usually include some hydroxylation products of the `starting ethylenic compound) also formed in the reaction. While it is usually preferred to mix all the reactants at once,

thereis sometimes an advantage in rst mixing the primary or secondary alcohol reactant and the ethylenic compound in those cases where the alcohol and ethylenic compound are different compounds, i. e. where ethylenic alcohols are not being used as combined alcohol and ethylenic compound, and then adding the peroxide portionwise to the mixture over a suflicient period of time so that there is no undue rise in `temperature from the exothermic reaction, since if all the peroxide is added at the beginning there maybe a tendency in some cases for the `reaction to get out of hand. Where an ethylenic alcohol is to serve as both ethylenic reactant and primary or secondary alcohol, one can likewise mix the peroxide therewith either all at once or portionwise. For continuous operation, `a plurality of reactors in series through which the reaction mixture is passed can be used, or the reaction mixture can be continuously pumped through a tubular or other suitable form of reactor in which the proper tlow rate and temperature is maintained so as v to keep the reaction within the previously indicated ranges of conditions.

Any suitable peroxide hydroxylating agent can be used successfully in the new reaction. Most preferably, hydrogen peroxide is employed, but other inorganic peroxides or organic peroxides are effective. Sodium and barium peroxides and the like are examples of other inorganic peroxides which can be used when acidited to neutralize alkaline salts, while typical organic peroxides are, for instance, tertiary butyl hydroperoxide and the like. Mixed peroxides such as are obtained by partial oxidation of hydrocarbons, for example, as described in U. S. Patent 2,376,257, are another example of the peroxides which can be used in producing hydroxy ethers according to the invention. When using aqueous peroxides, we prefer to employ solutions of 80% or higher peroxide content, most preferably hydrogen peroxide of 90% to 100% concentration, although more dilute solutions, for example 30% hydrogen peroxide, can be used.

The reaction can be carried out with any type of ethylenic compound which can be aliphatic, alicyclic or heterocyclic ethylenic compounds which can contain arol" matic rings in the molecule. The ethylenic alcohols, which can be primary, secondary or tertiary alcohols, are especially advantageous starting materials. Examples of suitable alcohols are allyl alcohol, methyl vinyl carbinol,

methallyl alcohol, crotyl alcohol, allyl carbinol, ethyl vinyl carbinol, dimethyl vinyl carbinol, methyl isopropenyl carbinol, methallyl carbinol, the cyclopentenols and cyclohexenols, styryl carbinol, oleyl alcohol, and the like. When the ethylenic alcohol used is tertiary, it is necessary to have a primary or secondary alcohol present since it has been found that steric hindrance or other factors make tertiary alcohols ineiective etheritication agents in the present reaction. Ethylenic ethers, acids, esters, ketones, aldehydes and organic halides are other types of suitable starting ethylenic compounds. Examples of suitable ethylenic carboxylic acids are, for instance,

acrylic acid, methacrylic acid, crotonic acid, tiglic acid, oleic acid, maleic acid, etc., and esters thereof with any of the foregoing or other ethylenic alcohols or with saturated alcohols. When ethylenic aldehydes are used as starting materials, oxidation to acids may accompany the reaction so hydroxy ether acids may be produced. Examples of aldehydes which can thus be used are acrolein, methacrolein, crotonaldehyde, tiglic aldehyde, betamethylcrotonaldehyde, and the like. Suitable ethylenic lketones which can be converted to hydroxy and ethersubstituted ketones are methyl vinyl ketone, methyl allyl ketone, ethylidene acetone, methyl isopropenyl ketone, mesityl oxide, etc. Oleiins such as ethylene, propylene, the butylenes, the amylenes and higher homologues thereof, cyclopentene, cyclohexene, methyl cyclohexene; diolens such as butadiene, isoprene or other pentadienes, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, dicyclopentadiene, etc.; olenic halides such as allyl chloride, allyl bromide, allyl fluoride, methallyl chloride, crotyl bromide, crotyl iodide, Vand the like; ethers, as methyl allyl ether, ethyl allyl ether, methyl methallyl ether, diallyl ether, dimethallyl ether, allyl crotyl ether, etc., and especially the water-soluble ethers such as glycol monoallyl ether, glycerol monoallyl ether, and the like, are other suitable ethylenic starting materials for use in the reaction. Substitution products of the foregoing ethylenic compounds, for instance, halo-substitution products of the ethylenic alcohols, ethers, aldehydes and ketones having the halogen atom or atoms linked to nonethylenic carbon atoms, can likewise be successfully converted to hydroxy ethers by the process of the invention.

Drying oils, semi-drying oils and other ethylenic triglycerides, for example, linseed oil, tungoil, corn oil, soya bean oil, sesame oil, fish oils, etc. and the monoand di-ethylenic fatty acids obtainable therefrom, are especially useful starting materials which can be reacted ac- .droxy and ether groups at adjacent carbon atoms linked 1 by ethylenic bonds in the starting compound. High molecular weight polyethylenic compounds such as polymers vof butadiene, isoprene and the like, including natural and synthetic rubbers, etc.,v are another useful type ,of

startingV material for the reaction.

The primary or secondary alcohol which serves as the etherifying agent in the new reaction can likewise vary widely in character. Aliphatic saturated monohydric 'alcohols such as methanol, ethanol, normal or isopropanol, isobutanol, secondary butanol, decanol, lauryl and lstearyl alcohols, etc., are suitable. Cyclic alcohols, including cyclopentanol, cyclohexanol, benzyl alcohol, the pheuols, etc., are also effective. Polyhydroxy alcohols such as ethylene glycol, diethylene glycol, pentaerythritol, sorbitol, and the like can be used in the same way. As a general rule, primary or secondary alcohols having one to eighteen, preferably one to ten, carbon atoms per molecule have been found most advantageous, especially when used with the preferred ethylenic compounds of two to eighteen, most preferably three to twelve, carbon atoms p erV molecule.

The following examples further illustrate the process of the invention:

Example l Allyl alcohol was reacted with Y% hydrogen peroxide using a mole ratio of allyl alcohol to hydrogen peroxide of 13.5:1 and 5 grams of W03 per mole vof hydrogen peroxide. Inl foiirhours, reactionat 35 C. a 41%6911- version of hydrogenperoxide tomenoallyl glycerol ether and a 15% conversion to glycerol was obtained. When a mole ratio of allylalcohol to hydrogenperoxide of -2 5. :1 was used with 3 grams of,WQ3`penmoleoivhydrogen peroxide at 50? C., the conversion ot hydrogenperoxide to .monoallylglycerol ether was 70%.with 16% conversion .to glycerol and 10% to higher boiling products.

Trichloromethane: chlorophosphouic acid,` used `at, V60" C., was found to bean eiectivebutsloweracting Vcatalyst for the production o flrnonoallyl glycerolether by this reaction, the conversion ofi-,1202 being 651%, after 1 hour at 60 C.

Using crotyl alcohol instead of 'allylalcoholunder the sameconditions givesan equally goodyieldyol the monocrotyl-ether ofv methylglycerol. Similar. results are obtained using phosphotungeticlacid as'kthe catalyst.

i Example II i Amixture-of 1.08 grof tungstic. acid and100 ml, of

water was stirred and 'heatedito 70" C. and then 5ml. of 34% hydrogen peroxide was added to dissolve-theftuugstic acid. There was then added 300y n11., 254,l g. Y(4,138 moles), of allylalcohol followed lbythed ropyv'ise addition of the remaining hydrogen-peroxide(100 g., .1.0 mole of 34%, total) in 2.5 hours at 70 C. .After-standing over night at room temperature, there-Was 0,009 mole of peroxidelleft and 44.3. g.rof glycerol V(482% ;on,v.,0lf

Cuts No. 4 and No. 5 are glycerol allyl ether V.and represent a 17.6% conversion of H2O2. Cut No.. 5 was analyzed with the following results:

. Found Galed for .j ,C vHizOs C 54. 39 54.52. H-. i 8. 91 9.16. Br. No. g. Br/lOO g 113 121. Hydroxyl value, eq./100 1.392 1.513. Acidity, eq./100 g 0.001 0.00. Alpha-glycol value calcd as glycerol alpha- 83 2 {100 for alpha. allyl ether. 0 for beta.

Example III A mixture of 1.08 g.` of tungstic acid-aud 100-m1.of water was stirred and heatedto 70 C. T here were added 5 m1. of 34% hydrogen peroxide-to dissolve Ythe tungstic acid followed by 58 g. (1.0 mole) of allyl alcohol diluted to 300 ml. with methanol. The remaining hydrogen peroxide (100 g., 1.0 mole of 34%,-tot a.l) was added dropwise over a two and one-quarter hour period at 70 C. A-fter standing over night at room temperature there was 0.025 mole of peroxide remaining. "I'he reaction Vproduct was distilled under vacuumand a precut of- 418 g. of water, methanol and allyl alcohol removed, vfollowed by:

. .G, Cut No. 1, 88-104'? C. (5 mm.) V 23 Cut No. 2, 11G-114 C. 05 mm.) 23

Cut No. 1 was redistilled.

of hydrogen peroxide),

Y NOQ. .2. waa-added to. the-residue.`

Residue 5 Y Y1 Cut No. 4 analyzedas follows:

Example IV Cyclohexene, ethanol Vaud hydrogen peroxidelSO/,z aqueousgllzOz)` were reacted together using aY 1.5:25z1 mole ratioand IQgrams of tungstic acid catalystper rnole 'of hydrogen peroxide. kThe reaction was .more than complete in less than three hours at 50f C, and resulted in 40% conversion ofy hydrogenperoxide to' 2ethoxycyclohexano1 and 38% conversionv to; 1,2; cyclohexanediol.

From the reaction under the same conditions of cyclohexene with 90% hydrogenperoxide and tungstic acid in dry l isopropanol l solution Ythere, wasv obtained` 21% conversion of 2 -isopropylcyclohexanol. Under the sarne xyriditions, using 16.7,moles ofJmethanol per mole of cyclohexene, a 70%. Yield vof Z-methoxycyclohexanol(a mobile liquid, boiling ypoint 181,C.) Was .lobtained.together with a 1,6% yield of 1,2-cyclohexanediol, hasedon 'the-hydrogen Peroxidein 11/2 hours.

Whenter-tiarygbutyl alcohol was used with cyclohexene andV hydrogen peroxide 4under conditions identical Avyith the foregoing tests,no ether product could be foundgthe product being. exclusively 1,2-cyclohexanediol.

Example V The reaction of Z-butene with'90%A hydrogen peroxide and methanol,v using tungsticY acid catalyst, wasarried out at room temperature .with a mole ratio ofyolenlto alcohol toperoxideljof 1.5 :2 5 g1. The peroxide yyasconsumed in 18 hours and distillationnaiorded l43,9% yield 0f 3-methQXy-2-butanol. and a 10% yield 4.Off/Z.,3-b11tanediol, basedr on hydrogen peroxide.

Under Similar Conditions, .except usingiobutyienein place 0f 2-bute11ie, a goed yield. 0f isomeric menomethyl ethers ,0f Z-methyI-.LZ-propanediol is htfiiiiedl and...by Shaking propr/Iene in methanoisclutiodat 50 C. for f1.2 hours with 34% hydrogenperexide solution 4(fidele.ratio 2:10:1) 'and tupgrsticaid catalyst (10 grams per., mole there was obtained a 23% yield (based 011. hydrogen peroxide.) ,0f a mixture. 0f .2,-meth0xyiiropanol` and .lfmethoXy-.Z-propanol and.. a 14%. yield of ,propylene glycol. These yields canbeimproved by operating .under pressure.

Example V1 A solution of 210 g., (1.5, moles) of 1decene (B: l?. -171 C.), 38.0 g. (1.0 mole) of 90% hydrogen peroxide, and 10 g.u of tungstic acid in '800 g. (25 molesljofmethanol was stirred at ,S5-60 C. for four .hours at which Atime over 90% of the peroxide had been consumedg t asoman Distillation through a two-foot packed column afforded 85 g. (0.61 mole) of recovered 1-decene and 102 g. of a mixture of 2-methoxydecanol1 and l-methoxydecanol- 2, B. P. 80-90 C. (1 mm.) (62% yield based on oleiin Converted). Crude 1,2-decanediol, B. P. 143-158 C., was obtained in 14% yield. n g

The reaction of 1-dodecene (1.5 moles) with hydrogen peroxide (1.0 moleof 34%) and tungstic acid (10 grams) in ethanol solution (14 moles) at 40- 50V C. kfor 6 hours gave 4a 23% conversion of olefin to hydroxyethoxydodecane, apparently 1-ethoxy-2-dodecanol, and crude 1,2-diol. When tertiary butyl alcohol was used in place of ethanol, no hydroxy ether was found among the products.

Example VII l66-172 C./1 mm), 30'g..(0.30"mole)-of 34% hydrogen peroxide, and 5 g. of tungstic acid in 300 ml. of methanol was stirred at 45450" C. for 3 hours, at which time one molar equivalent` of peroxide had been consumed.` The reaction mixture was poured into a liter of water Vcontaining 2 g. of sodium carbonate and extracted With 300 ml. of benzene; The benzene extract was Washed with water and concentrated to a crude residue of 77 g. Claisen distillation afforded 60 g. of product (70% yield), B. P. 20G-235 C. (5 mm.), the analysis of which indicated it to contain 43% W. methyl 9,10- dihydroxystearate and 48% w. methyl 9(10)hydroxy (9)-methoxystearate. Found: C, 69.0; H, 11.6;.alphaglycol value, 0.13 mole/ 100 g.; alkoxy value, 0.41 eq./ 100 g.

Fish oils and polyisobutylenes reacted under similar conditions, using methanol as the alcohol, give mixed polymethoxy-polyhydroxy products.

Example VIII 1;2 moles of cyclohexene and 1.0 mole of 90% hydrogen peroxide in 500 ml. of methanol were stirred at 55 C. with one milliliter of sulfuric acid as catalyst. After eleven hours, 85% of the peroxide had been consumed. Distillation resulted in the recovery of Z-methoxycyclohexanol in 60% yield, based on the 0.84 mole of cyclohexene converted. There was also obtained a. 14% yield of higher boiling material, chietly 1,2-cyclohexanediol.

By the use of phenol and benzyl alcohol in place of methanol in this reaction, Z-phenoxycyclohexanol and 2- benzyloxycyclohexanol, respectively, are obtained in the same way.

We claim as our invention:

1. A process of producing an unsymmetrical-hydroxy ether which comprises reacting an ethylenic compound, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with an alcohol having at least one hydrogen atoml directly attached to the carbinol carbon atom and withV hydrogen peroxide under the catalytic iniiuence of not more than 0.075 mole per mole of hydrogen peroxide employed of a strong acid which has an ionization constant for the first hydrogen greater than 1.86)(10-5 at 25 C. and reacts with hydrogen peroxide to form a peracid, the mole ratio of said alcohol to hydrogen peroxide being at least 2. A process of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic compound, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with a saturated alcohol having at least one hydrogen atom directly attached to the carbinol carbon atom and with hydrogen peroxide under the catalytic iniluence of not more than 0.075 mole per mole of hydrogen peroxide employed of a Astrong inorganic acid which has an ionization constant for the lirst hydrogen greater than 1.86 105 at 25 C.

and reacts with hydrogen pero `de to form a peracid, thev mole ratio of said valcohol to hydrogen peroxide being at least10z1 and the mole ratio of said alcohol to said ethylenic compound being at least about v10: 1.

3. Aprocess of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic alcohol, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with a saturated alcohol having at least one hydrogen atom directly attached to the carbinol carbon atom and with hydrogen peroxide in the presence of a catalytic amount not greater than 0.075 mole per mole of hydrogen perox# l ide employed of a strong inorganic peracid catalyst which A solution of 74 g. (0.25 mole) of methyl oleate (B. VP.,

has an ionization constant for the iirst hydrogen greater than 1.86 10*5at 25 C., the mole ratio of said satu. rated alcohol to hydrogen peroxide being at least 10:1 and the mole ratio of said saturated alcohol to said ethylenic alcoholbeing at least about 10: 1.

4. A process in accordance with claim 3 wherein the mole ratio of said ethylenic alcohol to said hydrogen peroxide is about 10:1 to about 50: 1.

y 5. A process of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic compound free from hydroxyl groups, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with an alcohol having at least one hydrogen atom linked directly to the carbinol carbon atom and with hydrogen peroxide under the catalytic influence of a catalytic amount not greater than 0.075 mole per mole of hydrogen peroxide employed of a strong inorganic acid which has an ionization constant for the lirst hydrogen greater than 1.86)(10-5 at 25 C. and reacts with hydrogen peroxide to form a peracid, the mole ratio of said alcohol to hydrogen peroxide being at least 10:1 and the mole ratio of said alcohol to said ethylenic compound being at least about 10: 1.

6. A process of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic hydrocarbon, wherein the valencies or"V the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with an alcohol having at least one hydrogen atom linked directly to the carbinol carbon atom and with hydrogen peroxide in the presence of a catalytic amount within the range of about 0.005 to 0.075 mole per mole of hydrogen peroxide of a strong inorganic peracid catalyst which has an ionization constant for the rst hydrogen greater than 1.86X10-5 at 25 C., the mole ratio of said alcohol to hydrogen peroxide being at least 10:1 and the mole ratio of said alcohol to said ethylenic compound being at least about 10:1.

7. A process in accordance with claim 6 wherein the ethylenic hydrocarbon is a cyclo-olefin.

8. A process in accordance with claim 6 wherein the alcohol is a saturated primary monohydric alcohol having 1 to 3 carbon atoms per molecule.

9. A process of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic hydrocarbon, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, with an alcohol having at least one hydrogen atom linked directly to the carbinol carbon atom and with hydrogen peroxide in the presence of tungstic acid catalyst, the mole ratio of said alcohol to hydrogen peroxide being at least 10:1 and the mole ratio of said alcohol to said ethylenic compound being at least about 10:1.

10. A process of producing an unsymmetrical hydroxy ether which comprises reacting an ethylenic alcohol, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, having at least one hydrogen atom directly attached to the 9 carbinol carbon atom and a peroxide in a mole ratio of at least 10:1 in the presence of a strong inorganic peracid catalyst which has an ionization constant for the rst hydrogen greater than 1.86 105 at 25 C., the mole ratio of water to said alcohol being not more than 4: 1.

11. A process of producing an unsymmetrical ether of an ethylenic primary alcohol, wherein the valencies of the ethylenically doubly bonded carbon atoms are each taken up by a member of the group consisting of the hydrogen and carbon atoms, and a trihydric alcohol which comprises reacting said ethylenic primary alcohol with hydrogen peroxide, the mole ratio of said primary alcohol to hydrogen peroxide being at least 10:1 in the presence of a tungstic acid hydroxylation catalyst, the mole ratio of water to said alcohol being not more than 4: 1.

12. A process of producing an unsymmetrical hydroxy ether which comprises reacting a mono-ethylenic monohydrc aliphatic alcohol having at least one hydrogen atom attached to the carbinol carbon atom `and 3 to 18 carbon atoms per molecule with hydrogen peroxide in the presence of tungstic acid, the mole ratio of said alcohol to hydrogen peroxide being about 10:1 to 50:1 whereby two moles of said alcohol react with one mole of said peroxide according to the equation:

where the Rs represent alkyl groups or hydrogen atoms, R1 represents an alkylene radical, and n is a positive whole number having a maximum value of two.

13. A process of producing a monoallyl ether of glycerol which comprises reacting allyl alcohol with hydrogen peroxide in the presence of tungstic acid using a mole ratio of allyl alcohol to hydrogen peroxide of at least 10:1.

14. A process of producing a monoalkyl ether of glyc- 10 erol which comprises reacting a saturated aliphatic alcohol having at least one hydrogen atom attached to the carbinol carbon atom, allyl alcohol and hydrogen peroxide in the ratios of about 10 to about 50 moles of said saturated alcohol and about 0.5 to about 4 moles of allyl alcohol per mole of hydrogen peroxide in the presence of tungstic acid at about 20 C. to 100 C.

15. A process in accordance with claim 14 wherein the saturated alcohol is a primary alcohol of one to eighteen carbon atoms.

16. A process in accordance with claim 14 wherein the saturated alcohol is a secondary alcohol of three to eighteen carbon atoms.

17. A process of producing a 2-alkoxycyclohexanol which comprises reacting a monohydric alcohol having 1 to 3 carbon atoms per molecule and at least one hydrogen atom attached to the carbinol carbon atom, cyclohexene and hydrogen peroxide in the presence of tungstic acid catalyst using a mole ratio of said alcohol to hydrogen peroxide of at least 10:1 and a mole ratio of cyclohexene to hydrogen peroxide of 1:1 to 2:1.

18. A process of producing Z-methoxycyclohexanol which comprises reacting methanol, cyclohexene and hydrogen peroxide in a mole ratio of 10 to 35 moles of methanol and 1 to 2 moles of cyclohexene per mole of hydrogen peroxide in the presence of tungstic acid.

References Cited in the le of this patent UNITED STATES PATENTS 2,373,942 Bergsteinsson Apr. 17, 1945 2,414,385 Milas Jan. 14, 1947 2,510,905 Raczynsk June 6, 1950 2,714,602 Abbott Aug. 2, 1955 OTHER REFERENCES Lespieau et al.: Compte rendu, Vol. 146 (1908), p. 1037. Swern: Chem. Reviews, vol. (August 1949), pp. 5, 25-30. 

1. A PROCESS OF PRODUCING A UNSYMMETRICAL HYDROXY ETHER WHICH COMPRISES REACTING AN ETHYLENIC COMPOUND, WHEREIN THE VALENCIES OF THE ETHYLENICALLY DOUBLY BONDED CARBON ATOMS ARE EACH TAKEN UP BY A MEMBER OF THE GROUP CONSISTING OF THE HYDROGEN AND CARBON ATOMS, WITH AN ALCOHOL HAVING AT LEAST ONE HYDROGEN ATOM DIRECTLY AT TACHED TO THE CARBINOL CARBON ATOM AND WITH HYDROGEN PEROXIDE UNDER THE CATALYTIC INFLUENCE OF NOT MORE THAN 0.075 MOLE PER MOLE OF HYDROGEN PEROXIDE EMPLOYED OF A STRONG ACID WHICH HAS AN IONIZATION CONSTANT FOR THE FIRST HYDROGEN GREATER THAN 1.86X10-5 AT 25*C. AND REACTS WITH HYDROGEN PEROXIDE TO FORM A PERACID, HE MOLE RATIO OF SAID ALCOHOL TO HYDROGEN PEROXIDE BEING AT LEAST 10:1.
 18. A PROCESS OF PRODUCING 2-METHOXYCYCOLHEXANOL WHICH COMPRISES REACTING METHANOL, CYCLOHEXENE AND HYDROGEN PEROXIDE IN A MOLE RATIO OF 10 TO 35 MOLES OF METHANOL AND 1 TO 2 MOLES OF CYCLOHEXENE PER MOLE OF HYDROGEN PEROXIDE IN THE PRESENCE OF TUNGSTIC ACID. 